This invention relates to a method for suppressing halide volatility during the calcination of zirconium-fluoride nuclear reprocessing waste solutions. More particularly, this invention relates to an improvement in the present method of suppressing halide volatility of adding calcium nitrate to the solution prior to calcination.
The chemical reprocessing of spent nuclear reactor fuel elements to recover the unburned nuclear reactor fuel material generates large volumes of aqueous solutions containing radioactive wastes. In addition to the large volumes produced, the aqueous waste solutions are extremely corrosive and present difficult problems in their handling and storage. Since it is necessary to store these radioactive wastes for long periods of time to permit decay of the radioactive constituents in the waste, the aqueous wastes are converted to a solid form which not only occupies less volume than the corresponding liquid wastes, but is less corrosive and easier to handle and store. One method by which these aqueous radioactive wastes are converted to solid form is by calcining in a fluidized bed in the Waste Calcining Facility at the Idaho Chemical Processing Plant located at the United States Department of Energy's Idaho National Engineering Laboratory in southeastern Idaho. The aqueous radioactive waste solutions are transported through pipelines from makeup vessels to the Waste Calcining Facility where the aqueous solutions are sprayed into the fluidized bed through spray nozzles mounted in the walls to be calcined into a solid for storage.
The composition of nuclear reactor fuels varies depending upon the type of reactor for which the fuel is intended. So also do the waste solutions resulting from reprocessing the fuel vary in composition, each solution presenting unique problems with regard to waste disposal. For example, it is necessary to dissolve irradiated zirconium-containing fuels in hydrofluoric acid for reprocessing. The reprocessing of these fuels results in the formation of two different waste solutions for which disposal must be provided. The one solution referred to as the first-cycle zirconium fluoride waste contains in addition a trace amount of chloride in addition to aluminum and other elements and compounds. The other solution -- second cycle waste -- contains fluoride, chloride, sodium and aluminum along with other values and is a composite waste which also includes radioactive waste from processing other fuels, operation ICPP support facilities, plant floor drains, process equipment and non-ICPP facilities located at the Idaho National Engineering Laboratory. For purposes of disposal, the first cycle waste is calcined by itself or it may be mixed with second cycle waste at a ratio of 3 to 1 by volume to form a blend. This is done to facilitate disposal of second cycle waste which, because it contains sodium nitrate, presents special disposal problems. However, calcining releases the fluorides and chlorides present in the solutions as volatile corrosive gases which, because they are highly corrosive, are very detrimental to equipment and may be damaging to the environment should they be released.
It is known that adding calcium nitrate to the waste solutions before calcining the solutions will suppress the volatility of the fluoride to acceptable levels which can then be removed from the calciner off-gas by scrubbing equipment. However, the addition of calcium nitrate to the waste has little suppressive effect upon the chloride which, although present in the waste solutions in only relatively small amounts builds up in the fluidized bed of the calciner over a long period of operation, so that the quantity, in time, becomes significant. The addition of calcium nitrate to the waste solutions also results in the formation of a gelatinous solid. This solid, which is a hydrated calcium fluorozirconate, clogs transfer piping and calciner spray nozzles and generally disrupts calciner operation by increasing down-time for cleanup. The substitution of magnesium nitrate for calcium nitrate has been tried, and although it eliminates the formation of gelatinous solids while maintaining fluoride volatility suppression at acceptable levels, it has insufficient effect upon chloride volatility. When magnesium nitrate is added to first cycle waste, a calcine is produced which is very soft and breaks easily into fines during fluidized bed operation, plugging and bridging calciner off-gas and transport systems.